Halogenated bicyclic acid keto esters



United States Patent 3,371,108 HALOGENATED BICYCLIC ACID KETO ESTERIsrael J. Dissen, Chicago, IlL, assignor t0 Velsicol ChemicalCorporation, Chicago, 111., a corporation of Illinois No Brewing. FiledAug. 21, 1964, Ser. No. 391,312 Claims. (Cl. 260468) wherein X isselected from the group consisting of chlorine, bromine and fluorine; Yis selected from the group consisting of hydrogen, chlorine, bromine andfluorine; n is an integer from 0 to l; R and R are alkylene groupscontaining from one to ten carbon atoms; R is an alkyl group containingfrom one to ten carbon atoms; R and R are independently selected fromthe group consisting of hydrogen and an alkyl group containing from oneto ten carbon atoms; and R is independently selected from the groupconsisting of hydrogen, an alkyl group containing from one to ten carbonatoms and o H H (R ..o01t-c--R wherein R, R R and n are as definedabove.

The compositions of the present invention are useful as plasticizers,particularly for vinyl resins. These new compositions when used asplasticizers, impart flame and fire retardance to the final resincomposition or end product.

Therefore, it is one object of the present invention to prepare newcompositions of matter useful in the production of products of vinylresins.

Another object of the present invention is the preparation of newhalogenated compositions of matter.

Another object of this invention is to provide plasti cizcrs for vinylresins.

Still another object of this invention is to provide plasticizers forvinyl resins which impart flame and fire retardance to the resincomposition.

These and other objects and advantages of the present invention willbecome apparent from the ensuing description.

The compositions of the present invention are remarkably eflective asplasticizers when mixed with thermoplastic resins, such as polyvinylchloride, chlorinated polyethylene, polyvinyl acetate, vinylchloride-vinylidene chloride copolymers, and the like. Thiseffectiveness is believed to be due at least in part to the presence ofthe keto group on the alcohol portion of the esters of the presentinvention. The compositions of the present invention can be added in anamount ranging between 120% by weight based on the weight of the resin.

The compounds of the present invention can be readily prepared from analiphatic keto alcohol and a polyhalogenated norbornene acid. The twoingredients are esterified to form the compounds of the presentinvention. The esterification is preferably performed in the presence ofan esterification catalyst, and most preferably in the presence of acidcatalysts such as para-toluene sulfonic acid, sulfuric acid,hydrochloric acid, boron-trifluoride, aluminum trichloride and the like.Although the esterification will take place in the absence of thecatalyst, the rate is slow and hence the use of catalyst is preferred.Only catalytic amounts of catalyst such as from 0.005% to about 5% byweight of the reactants, are required to accelerate the reaction. Theesterification proceeds with the formation of water. It is preferred toremove the water as it is formed by suitable means, such as byazeotroping a mixture of the water with an organic substance in whichthe water is relatively immiscible. For this purpose it is preferred toemploy a suitable quantity of an organic liquid, such as toluene,xylene, benzene, heptane, and the like, and perform the esterificationat reflux so as to remove the water as it is formed.

Alternatively, the compounds of the present invention can be readilyprepared by first esterifying the aliphatic keto-alcohol with anunsaturated acid, and then adducting the resulting unsaturated ester ordiester with the appropriate halogenated cyclopentadiene. As in thefirst method, the esterification is preferably performed in the presenceof an esterification catalyst, most preferably an acid catalyst, such asthose heretofore described. An organic liquid is also preferablyemployed to aid in removing water formed during the esterificationreaction. The adduction reaction can be preformed by heating thehalogenated cyclopentadiene with the unsaturated ester of diester in themanner described for the preparation of the norbornene acid.

The compounds of the present invention can also be prepared readily byfirst preparing the acid chloride of the polyhalogenated norborneneacid, and then reacting the acid chloride with the aliphatic ketoalcohol. The acid chloride of the polyhalogenated norbornene acid can beprepared readily by reacting the acid with a suitable chlorinatingagent, such as phosphorus pentachloride, and removal of by-productoxychlorides. The acid chloride and the aliphatic keto alcohol react inthe manner heretofore described with heating and the removal of water asit is formed.

Suitable norbornene acids which can be employed in the manner describedabove can be readily prepared by reacting a polyhalogenatedcyclopentadiene with an unsaturated acid in a Diels-Alder adduction, asdescribed by Prill, J.A.C.S vol. 69, p. 62 (1947). Suitable halogenatedcyclopentadiene ingredients are hexachlorocylopentadiene,pentachlorocyclopentadiene, tetrachorocyclopentadiene,hexabromocyclopentadiene, pentabromocyclopentadiene,tetrabromocyclopentadiene, hexafluorocyclopentadiene,5,S-difluorotetrachlorocyclopentadiene, and the like. Exemplary of thesuitable unsaturated acid and diacids or anhydn'des thereof, which canbe adducted with the polyhalogenated cyclopentadienes to yield thenorbornene ingredient, or first esterified and then adducted, to form rthe desired compounds of this invention, are: acrylic acid,

crotonic acid, vinylacetic acid, angelic acid, tiglic acid, 3-pentenoicacid, allylacetic acid, undecylinic acid, oleic acid, maleic acid,citraconic acid, cis-glutaconic acid, and the like.

Aliphatic keto alcohols which can be utilized in the preparation of thecompounds of the present invention are exemplified by: pyruvic alcohol,4 hydroxy 3- butanone, 4 hydroxy 2 butanone, 4 hydroxy 3- methyl 2butanone, 4 hydroxy 2 pentanone, 4- hydroxy 4 methyl 2 pentanone, 4hydroxy 3- methyl 2 pentanone, 5 hydroxy 2 pentanone, 6-hydroxy-2-hexanone, and the like.

The following examples are set forth to illustrate but not limit thepreparation of the compounds of the present invention, and in eachexample there can be substituted therein other reactants within thepreviously described scope of the invention.

EXAMPLE 1 Preparation of 1,2,3,4,7,7hexachloro-Z-norbornen-5,6-dicrzrbnyl chloride Chlorendic acid(1,2,3,4,7,7-hexachloro-2-norbornen' 5,6-dicarboxylic acid) (371 g; 1.0mol.) and phosphorus pentachloride (260 g; 1.25 moles) were placed intoa one liter, three-neck, round-bottom flask equipped with a mechanicalstirrer, internal thermometer and reflux condenser attached to aDean-Stark tube. The flask was heated and the temperature of thecontents increased to about 100 C. Where the contents became liquid. Thecontents of the flask were maintained at reflux (150 C.) by drawing offby-product phosphorus oxychloride from the Dean-Stark tube. After thecontents of the flask began to darken, the heating was stopped, and thecontents allowed to cool. Phosphorus oxycnloride was removed from thereaction mixture by heating to 120 C. under vacuum created by a wateraspirator. The reaction mix ture was distilled in vacuo and1,2,3,4,7,7-hexachloro- 2,-norbornen-5,6-dicarbonyl chloride wascollected as the distillate, distilling at 150-160 C. at about 1 mm.mercury pressure.

EXAMPLE 2 Preparation of his (3-kezobulyl) l,2,3,4,7,7-hcxac!1Zoro-2-n0rb0rnen-5,6-dicarb0xylate Anhydrous sodium carbonate (170 g; 1.6moles), anhydrous magnesium sulfate (100 g; 0.8 mol), 1,2,3,4, 7,7hexachloro 2 norbornen-S,6-dicarbonyl chloride (170.4 g.; 0.4 mol),prepared in Example 1, and benzene (600 ml.) were placed in a one liter,three-neck, roundbottom flask equipped with a mechanical stirrer,internal thermometer, reflux condenser and drop-ping funnel. 4hydroxy-Z-butanone (17.6 g.; 0.2 mol) was charged to the droppingfunnel. The contents of the flask were heated to 80 C. and the4-hydroXy-2-butanone added to the flask dropwise. After most of the4-hydroxy-2- butanone was added, the reaction mixture began to foam, andhad to be alternately cooled and warmed several times in order tocontrol the foaming. The reaction mixture was maintained at 70-80 C. forabout /2 hour after the addition was complete. The mixture was thencooled and the solid precipitate filtered oil. The filtrate was washedtwice with water and then with aqueous sodium bicarbonate solution, anddried over anhydrous magnesium sulfate. Benzene was removed from thefiltrate by heating on a steam bath in vacuo leaving as a dark yellowliquid the desired product bis(3-ketobutyl) 1,2,3,4,7,7 hexachloro2-norbornen-5,6-dicarboxylate. The product was dissolved in diethylether, washed twice with sodium carbonate, and dried. The diethyl etherwas removed by heating on a steam bath in vacuo, leaving the purifiedcompound as a yellow liquid having a refractive index of 1.5264 at 23.8C.

EXAMPLE 3 Preparation of 3-ket0butyl 1,2,3,4,7,7-hcxachl0r0-2-norbornen-S-carboxylate Anhydrous sodium carbonate (170 g; 1.6 moles),anhydrous magnesium sulfate (100 g; 0.8 mol), 4-hydroxy-2-butanone (35g.; 0.1 mol) and benzene (300 ml.) are charged to the flask described inthe previous example. 1,2,3,4,7,7 hexachloro-2-norbornen-S-carbonylchloride (145 g; 0.4 mol) prepared from 1,2,3,4,7,7-hexachloro-Z-norbornen-S-carboxylic acid as described in Example 1,dissolved in benzene (300 ml.) is placed in the dropping funnel andadded dropwise to the flask after the contents have been heated to about80 C. Upon completion of the addition the reaction mixture is maintainedat 80 C. for about /2 hour, after which the reaction mixture is cooled,and the precipitate filtered OH. The filtrate is washed with water andaqueous sodium bicarbonate solution, and dried over anhydrous magnesiumsulfate. Benzene is removed from the filtrate by heating on a steam bathin vacuo leaving 3-ketobutyl1,2,3,4,7,7-hexachloro-2-norbornen-5-carboxylate, as the residue.

The procedure detailed in the above examples can be utilized to prepareother compounds within the scope of the invention. Given in the examplesbelow are the necessary reactants from which the named compounds of thepresent invention can be prepared. The first reactant is the diene whichis reacted with the unsaturated acid reactant yielding the norborneneacid which can be reacted with the third reactant, the keto alcohol,either directly or through the acid chloride, to form the namedcompound.

EXAMPLE 4 T etrachlorocyclopentadiene+ acrylic acid+4-hydroxy-Z-butanonc: -ketobutyl 1,2,3,4-tetrachloro-2-norbornen- S-carboxylate.

EXAMPLE 5 Hexachlorocyclopentadiene+acrylic acid+4-hydroxy-2-pentanone:3-keto-1-methylbutyl1,2,3,4,7,7-hexachloro-2-norbornen5-carboxylate.

EXAMPLE 7 Hexabrornocyclopentadiene+acrylic acid-t-4-hydroxy-2-butanone=3-ketobutyl 1,2,3,4,7,7-hexabromo-2-norbornen-S-carboxylate.

EXAMPLE 8 Hexachlorocyclopentadiene+crotonic acid-l-pyruvic alcohol=2ketopropyl 1,2,3,4,7,7-hexachloro-6-methy1-2- norbornen-S-carboxylate.

EXAMPLE 9 Hexachlorocyclopentadiene+vinylacetic acid+4hydroxy-Z-butanonc:3-ketobutyl 1,2,3,4,7,7-hexachloro-2-norbornen-S-acetate.

EXAMPLE l0 Tetrachlorocyclopentadiene+B-pentenoic acid+4 hydroxy 2butanone=3-ketobutyl l,2,3,4-tetrachloro-'6-methyl-2-norbornen-5-acetate.

EXAMPLE 1 1 Tetrabromocyclopentadiene+allylacetic acid+4 hydroxy4-methyl-2-pentanone:3-keto-1,l-dimethylbutyl1,-2,3,4-tetrabromo-2-norb0rnen-5-propionate.

EXAMPLE 12 Hexabromocyclopentadiene+maleic acid-tt-hydroxy-2-butanone:bis(3-ketobutyl) 1,2,3,4,7,7-hexabromo2-norbornen-5,o-dicarboxylate.

5 EXAMPLE 13 lentachlorocyclopentadiene+maleic acid+4-hydroxy-2-pentanone=bis(S-keto-l-methylbutyl)1,2,3,4,7-pentachloro-Z-norbornen-S,6-dicarboxylate.

EXAMPLE 14 EXAMPLE 15 Hexachlorocyclopentadiene-l-citraconic acid+4hydroxy-2-butanone=bis (B-ketobutyl)l,2,3,4,7,7-hexachloro-5-methyl-2-norbornen-5,G-dicarboxylate.

The following example ilustrates the effectiveness of the compounds ofthe present invention as a plasticizer for vinyl resins. The plasticizedresin thus obtained possesses flame retardant properties due to thecompounds of this invention. Although a specific compound of the presentinvention is utilized in Example 16, other compounds within the scope ofthe present invention can be successfully substituted therefor.

EXAMPLE 16 Use of the compounds 0] the present invention as aplasticizer Polyvinyl chloride resin Marvinol VR23 marketed by theUnited States Rubber Company (100 parts), product of Example 1 (50parts) and a barium-cadmium stabilizer (2.5 parts) are roll milled at300 F. and pressed into a sheet at 350 F. The sheet thus obtainedpossesses desirable hardness, tensile strength, heat stability, inaddition to the fire resistance required for many vinyl resinapplications.

The compounds of the present invention are also useful in numerous otherapplications, such as a lubrication oil additive, as a hydraulic fluid,as a solvent for resins, as a biocide, particularly as an insecticide,and as an intermediate in the production of numerous compounds, such asnitroso compounds, ketals and the like.

6 I claim: 1. A compound of the formula wherein X is selected from thegroup consisting of chlorine, bromine and fluorine; Y is selected fromthe group consisting of hydrogen, chlorine, bromine and fluorine; n isan integer from 0 to 1; R and R are alkylene groups containing from oneto ten carbon atoms; R is an alkyl group containing from one to tencarbon atoms; R and R are independently selected from the groupconsisting of hydrogen and an alkyl group containing from one to tencarbon atoms; and R is independently selected from the group consistingof hydrogen, an alkyl group containing from one to ten carbon atoms ando o (R n O R R wherein R, R R and n are as described above.

2. Bis(3 -ketobutyl)1,2,3,4,7,7-hexachloro-2-norbornon-5,6-dicarboxylate.

3. 3 -ketobutyl 1,2,3,4,7,7-hexachloro-2-norbornen-5- car'boxylate.

4. Bis(3 ketobutyl) nen-5,-6-dicarboxylate.

5. 3 -ketobuty1 1,2,3,4,7,7-hexachloro-2-norbornen-5-1,2,3,4,7,7-hexabromoe2-norboracetate.

References Cited UNITED STATES PATENTS 3,278,580 10/1966 Worsley 26046'8LORRAINE A. WEINBERGER, Primary Examiner. P. I. KILLOS, AssistantExaminer.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,371,108 February 27, 1968 Israel J. Dissen It is certified that errorappears in the above identified patent and that said Letters Patent arehereby corrected as shown below:

Column 1, lines 33 and 34, and column 6, lines 3 to 9, for that portionof the formulas reading -0-R -cread -0-R -c- Signed and sealed this 22ndday of July 1969.

(SEAL) Attest:

Edward M. Fletcher, Jr.

Attesting Officer WILLIAM E. SCHUYLER, JR.

Commissioner of Patents

1. A COMPOUND OF THE FORMULA